类普鲁士蓝衍生物活化过一硫酸盐降解罗丹明B研究

doi:10.11949/0438-1157.20240371

摘要/Abstract

摘要：

采用铜铁类普鲁士蓝衍生物（Cu_nFe₁-PBAs）活化过一硫酸盐（PMS）降解罗丹明B（RhB），考察铁铜摩尔比、催化剂投加量、PMS与RhB的摩尔比、起始pH和水中常见离子对RhB降解的影响。结果表明：Cu₂Fe₁-PBAs可以有效活化PMS降解RhB。在RhB浓度为20 mg/L，Cu₂Fe₁-PBAs用量为0.6 g/L，PMS浓度为0.513 g/L，碱性条件时最有利于RhB降解。NO₃^-、HCO₃^-、Cl^- 促进RhB的降解，SO₄^2-抑制RhB的降解。硫酸根自由基（SO₄^-·）、羟基自由基（·OH）、单线态氧（¹O₂）和超氧自由基（·O₂^-）均参与Cu₂Fe₁-PBAs活化PMS降解RhB反应过程中。

关键词: 类普鲁士蓝衍生物, 过一硫酸盐, 罗丹明B, 单线态氧, 超氧自由基

Abstract:

Rhodamine B (RhB) was degraded by Peroxymonosulfate (PMS) activated by Cu_nFe₁-PBAs. The effects of the molar ratio of iron to copper, the amount of catalyst, the molar ratio of PMS to RhB, initial pH and common ions in water on RhB degradation were investigated. The results showed that Cu₂Fe₁-PBAs could effectively activate PMS to degrade RhB. RhB degradation was most favorable under alkaline conditions when RhB concentration was 20 mg/L, Cu₂Fe₁-PBAs dosage was 0.6 g/L, and PMS concentration was 0.513 g/L. NO₃^-, HCO₃^-and Cl^- promoted the degradation of RhB, while SO₄^2-inhibited the degradation of RhB. Sulfate radical (SO₄^-·), hydroxyl radical (·OH), singlet oxygen (¹O₂) and superoxide radical (·O₂^-) all participated in the RhB degradation of Cu₂Fe₁-PBAs activated PMS.

Key words: Cu_nFe₁-PBAs, peroxymonosulfate, rhodamine B, singlet oxygen, superoxide radical

中图分类号:

TQ 028.8

陈贵梅, 谢雨芸, 杨有威, 高艳, 王春英. 类普鲁士蓝衍生物活化过一硫酸盐降解罗丹明B研究[J]. 化工学报, DOI: 10.11949/0438-1157.20240371.

Guimei CHEN, Yuyun XIE, Youwei YANG, Yan GAO, Chunying WANG. Degradation of Rhodamine B by Peroxymonosulfate activated by Prussian blue analogue derivatives[J]. CIESC Journal, DOI: 10.11949/0438-1157.20240371.

图/表 15

图1 铁铜摩尔比例对RhB降解效果的影响注:实验条件:[Cu2Fe1-PBAs]0=400 mg/L; [PMS]0=500 mg/L; pH0=5.16; [RhB]0=20 mg/L; 反应温度为25±2 ◦C

Fig.1 Effect of molar ratio of iron to copper on degradation of RhBReaction conditions: [Cu2Fe1-PBAs]0=400 mg/L; [PMS]0=500 mg/L; pH0=5.16; [RhB]0=20 mg/L; Temperature 25±2 ◦C

表1 其他可活化过一硫酸盐降解RhB的实验对比

Table 1 Comparison of other experiments for the degradation of RhB by activated peroxymonosulfate

催化方式	催化剂浓度(mg/L)	初始浓度（mg/L）	PMS（mg/L）	pH	反应时间（min）	去除率（%）
Cu₂Fe₁-PBAs	600	20.0	513	5.16	30	92.72	本文
磁性茶渣炭	213	40.0	302	5	80	98	[16]
紫外光下施氏矿物	500	4.79	307	——	45	93.7	[17]
黄铁矿	1000	20	307	5	180	99	[18]
铁酸铜	100	2.39	61	——	30	88.87	[19]
氧化铜纳米颗粒	500	50	614	7.5	60	93.38	[20]
兔粪生物炭	600	25	400	——	40	98	[21]

图2 Cu2Fe1-PBAs投加量对RhB降解的影响(a)和一级动力学模拟(b)注:Reaction conditions: [Cu2Fe1-PBAs]0=200-600 mg/L; [PMS]0=513 mg/L; pH0=5.16; [RhB]0=20 mg/L; Temperature 25±2 ◦C实验条件:[Cu2Fe1-PBAs]0=200-800 mg/L; [PMS]0=500 mg/L; pH0=5.16; [RhB]0=20 mg/L; 反应温度为25±2 ◦C

Fig.2 Effect of Cu2Fe1-PBAs dosage on RhB degradation (a) and the corresponding curves of pseudo-first order reaction kinetics (b)

图3 PMS投加量对RhB降解的影响(a)和一级动力学模拟(b)注:Reaction conditions: [Cu2Fe1-PBAs]0=600 mg/L; [PMS]0=128-1026 mg/L; pH0=5.16; [RhB]0=20 mg/L; Temperature 25±2 ◦C实验条件:[Cu2Fe1-PBAs]0=600 mg/L; [PMS]0=128-1026 mg/L; pH0=5.16; [RhB]0=20 mg/L; 反应温度为25±2 ◦C

Fig.3 Effect of PMS Dosage on RhB degradation (a) and the corresponding curves of pseudo-first order reaction kinetics (b)

图4 PMS的反应剩余注:实验条件:[Cu2Fe1-PBAs]0=600 mg/L; [PMS]0=128-1026 mg/L; pH0=5.16; [RhB]0=20 mg/L; 反应温度为25±2 ◦C

Fig.4 Residual degradation of PMSReaction conditions: [Cu2Fe1-PBAs]0=600 mg/L; [PMS]0=128-1026 mg/L; pH0=5.16; [RhB]0=20 mg/L; Temperature 25±2 ◦C

图5 催化剂四次循环催化效果注:实验条件:[Cu2Fe1-PBAs]0=600 mg/L; [PMS]0=513 mg/L; pH0=5.16; [RhB]0=20 mg/L; 反应温度为25±2 ◦C

Fig.5 Catalytic effect of four cycles of catalystReaction conditions: [Cu2Fe1-PBAs]0=600 mg/L; [PMS]0=513 mg/L; pH0= 5.16; [RhB]0=20 mg/L; Temperature 25±2 ◦C

图6 起始pH对RhB降解的影响注:实验条件:[Cu2Fe1-PBAs]0=600 mg/L; [PMS]0=513 mg/L; pH0=3-11; [RhB]0=20 mg/L; 反应温度为25±2 ◦C

Fig.6 Effect of initial pH on RhB degradationReaction conditions: [Cu2Fe1-PBAs]0=600 mg/L; [PMS]0=513 mg/L; pH0= 3-11; [RhB]0=20 mg/L; Temperature 25±2 ◦C

图7 紫外可见光光谱(a)不同初始pH反应30min后溶液的谱图； (b) 初始pH=11在不同反应时间下的谱图(实验条件：[Cu2Fe1-PBAs]0=600 mg/L; [PMS]0=513 mg/L; pH0=3-11; [RhB]0=20 mg/L; 反应温度为25±2 ◦C)

Fig.7 Ultraviolet-visible spectrum of catalytic degradation of RhB system at each pH after 30 min (a) and pH=11 with different reaction time (Reaction conditions: [Cu2Fe1-PBAs]0=600 mg/L; [PMS]0=513 mg/L; pH0= 3-11; [RhB]0=20 mg/L; Temperature 25±2 ◦C)

图8 共存阴离子对RhB降解的影响注:实验条件:共存阴离子浓度为5 mM; [Cu2Fe1-PBAs]0=600 mg/L; [PMS]0=513 mg/L; pH0=5.16; [RhB]0=20 mg/L; 反应温度为25±2 ◦C

Fig.8 Effect of co-existing anions on RhB degradationReaction conditions: coexisting anion 5 mM;[Cu2Fe1-PBAs]0=600 mg/L; [PMS]0=513 mg/L; pH0= 5.16; [RhB]0=20 mg/L; Temperature 25±2 ◦C

图9 (a)不同活性组分猝灭剂对RhB降解的影响（实验条件：猝灭剂浓度为50-1000 mM; [Cu2Fe1-PBAs]0= 600 mg/L; [PMS]0=513 mg/L; pH0=5.16; [RhB]0=20 mg/L; 反应温度为25±2 ◦C）；(b)TEMP的电子顺磁共振谱和(c,d) DMPO的电子顺磁共振谱

Fig.9 (a)Effects of different radical scavengers on RhB degradation (Reaction conditions: radical scavengers 50-1000 mM；[Cu2Fe1-PBAs]0=600 mg/L; [PMS]0=513 mg/L; pH0=5.16; [RhB]0=20 mg/L; Temperature 25±2 ◦C); EPR spectrums of (b)TEMP and (c,d)DMPO

图10 X射线衍射

Fig.10 XRD

图11 扫描电镜

Fig.11 SEM

图12 傅立叶变换红外吸收光谱

Fig.12 FTIR

图13 使用前后的Cu2Fe1-PBAs XPS（a），O（b），Fe（c）和Cu（d）

Fig.13 Cu2Fe1-PBAs XPS (a), O (b), Fe (c) and Cu (d) before and after the reaction

图14 自由基产生机理图

Fig.14 Free radical production mechanism diagram

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